Seven-membered intramolecular hydrogen bonding (7MHB) arrangements involving phenolic hydroxyl group donors have been investigated through Cambridge Structural Database (CSD) and literature mining, and the characterization of model compounds. The CSD reveals the numerous H-bond accepting functional groups that can participate in 7MHB when they are proximal to the phenolic –OH, including alcohols, amides, amines, ethers, N-containing heterocycles, ketones, N-oxides, phosphates, and phosphine oxides. The HB contacts are defined by Ophenol···N and Ophenol···O distances of ~ 2.7 Å, and two dihedral angles that fall within the range of typical peptide γ-turns. Two of the identified 7MHB motifs have been readily mapped onto the phloroglucinol (1,3,5-trihydroxybenzene) scaffold to provide eight model compounds; intramolecular hydrogen bonding involving all three hydroxyl groups is shown to persist in solution and the solid state for the compounds. Intramolecular 7MHB enforces non-planar conformations that should be useful when designing molecular hosts and catalysts.